The influence of working pressure, which is one of the most important parameters in the design of thermoelectric conversion system, on the heat transfer process and heat absorption of supercritical CO2 in the square heated duct is numerically studied. Under the calculated cases, two main vortices with opposite flow direction are formed at the inlet of the heated section. Accordingly, due to the effect of two main vortices, the local heat transfer coefficient profiles on bottom and up wall are M shaped. Meanwhile, it is founded that one wall temperature peak is presented near the inlet of heated duct. With the increase of working pressure, the wall temperature peak decreases gradually. For the safety of the system, it is better to choose 15 MPa as the working pressure due to the relatively low wall temperature peak and pressure. To evaluate the heat absorbed by working fluid, the one-dimensional steady heat transfer model is built. It is found that the absorbed heat changes non-monotonically and the maximum, namely 1080.11 W, is reached under 10 MPa. From the point of heat absorption, it is better to choose 10 MPa as working pressure.